Condensation of saturated hydrocarbons with chloroolefins



Patented July 31, 195! 7 I UNITED STATES PATENT OFFICE CONDENSATION 0F SATUBATED HYDRO- CABBONS WITH CHLOBOOLEFINS Louis Schmerling, Riverside, IIL, assign to Unlversal Oil Products Company, Chicago, 111., a

corporationot Delaware No Drawing. Application m. :0. 1950, Serial No. mass 10 0mm. (01. zen-s48) condensation of A polychlorooleflns, particularlypolychloromonooleflns in which each of the doubly bonded carbon atoms has at least one chlorine atom attached thereto, with saturated hydrocarbons containing more than two carbon atoms per molecule in the presence of a peroxy compound condensation catalyst. One molecule of the chloroolefln condenses with one molecule of the saturated hyd rocarbon with the elimination or evolution of one molecule of hydrogen chloride. The resultant productis unsaturated. In one embodiment my invention relates to a process which comprises reacting a saturated hydrocarbon containing more than two carbon atoms with a polychloroolefin at condensation conditions in the presence of a peroxy compound condensation catalyst.

In a more specific embodiment my invention relates to a process which comprisesreacting a saturated hydrocarbon containing more than two carbon atoms with a polychloromonoolefin having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a temperature at least as high as the initial decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants are in the liquid phase.

In another specific embodiment my invention relates to a process which comprises reacting a saturated hydrocarbon containing more than two carbon atoms with a polychloromonoolefln, in

- atoms bonded by univalent bonds to tour atoms.

. z I which each of the doubly bonded carbon atoms has at least one chlorine atdm attached thereto,

in the presence oi. a peroxy compound condensation catalyst and water and at a temperature at least as high as the initial decomposition temperature of the catalyst.

The saturated hydrocarbons that are utilizable in the process of this invention comprise paraflins containing more than two carbon atoms per molecule such as propane, normal butane, isobutane, normal pentane, isopentane, isooctane and the like, as well as cycloparaflins such as cyclopentane, cyclohesane, methylcyclopentane and the like. Cycloparaflins containing less than five carbon atoms in the ring generally are not utilizable in my process, since they are less stable than cyclopentanes and cyclohexanes and act more like oleflns.

The chlorooleflns that may be reacted with saturated hydrocarbons in the presence of peroxy compound condensation catalysts in accordance with my invention comprise chlorooleflns containing more than one chlorine atom per molecule. A preferred species comprises polychloromonoolefins in which both of the doubly bonded carbon atoms has at least one chlorine atom attached thereto. The chloroolefln may be either of the open chain or cyclic type. Examples of suitable chlorooleflns are 1.2-dichloroethylene, I

trichloroethylene, tetrachloroethylene, 1,2-dichloro-l-propene, 1,2-dichlorocyclohexene, and 1,1,2-trichloro-1-propene. It is essential that the chloroolefln contain at least two chlorine atoms per molecule, since monochlorooleflns do not give a condensation reaction of the type herein described. Similarly, polyhalooleflns other than polychoroolefins, do not give reactions of the type herein described. Polychlorooleflns such as 3,3,3wtrifluoro-l.2-dichloro-1-propene that contain one or more fluorine atoms attached to one or more saturated carbon atoms, i. e., carbon may be used in my process since the fluorine atoms in such compounds do not noticeably aflect the reactivity of the chlorine atoms.

The catalysts that may be used in the present process are .those which are capable of forming free radicals under the reaction conditions. These include peroxy compounds, by which is meant any compound capable of inducing the condensation of saturated hydrocarbons with chlorooleflns and which contains the bivalent radical-OO Examples of such compounds are the alkali metal and ammonium persulfates, perborates. and percarbonates; peracetic acid, persuccinic acid, dimethyl peroxide, diethyl peroxide, methyl ethyl peroxide, di-tertiary-butyl peroxide, di-propyl peroxide, acetyl benzoyl peroxide, acetyl peroxide, propionyl peroxide, butyryl peroxide, lauroyl peroxide, benzoyl peroxide, tetralin peroxide, urea peroxide, tertiary butyl perbenzoate,

tertiarybutyl hydroperoxide, and methylcyclohexyl hydroperoxide. The organic peroxy compounds constitute a preferred class of catalysts for use in this invention. Mixtures of peroxy compound catalysts may be employed. Only catalytic amounts ('1. e., less than stoichiometric amounts) need be used in my process. Among the other free radical forming catalysts which may be used are metal alkyls such as lead tetraethyl and diazonium compounds.

Hydrogen chloride is evolved in the condensation reactions herein disclosed. In cases where it is desirable to avoid radical changes in pH during the course of the reaction, small amounts of materials which have a battering action on the pH may be included in the condensation mixture. Since the condensations can be carried out satisfactorily in either an acid or an alkaline medium, many types of buffering agents can be used. For example, an alkaline pH can be maintained by the use of such builfers as borax, disodium phosphate. sodium carbonate, ammonium carbonate, sodium acetate, etc. For a pH below '1, such materials as acetic acid, propionic acid, and other organic acids, monosodium phosphate, sodium hydroxide+potassium acid phthalate, and the like may be used.

It is known that metal halides of the Friedel- Crafts type catalyze the condensation of isoparafllns with halooleflns, but a comparison of the results obtained with those catalysts and the results obtained with the peroxy compound catalysts herein disclosed, shows that there are marked differences. For example, in the condensation of isobutane with symmetrical dichloroethylene, the use of Friedel-Crafts metal halide catalyst yields a saturated chloride, name- 1y 1,1,2-trichloro-3,3-dimethylbutane. as well as hexane, a saturated hydrocarbon. On the other hand, the use of a peroxy compound catalyst yields l-chloro-3,3-dimethyl-1-butene, an unsaturated chloride, and hydrogen chloride. Again the condensation of cis or trans dichloroethylene with isobutane gives nearly equivalent yields with peroxides; whereas with Friedel- Crafts metal halides, the trans compound gives much lower yields than the cis. Finally, and probably most important, the use of peroxides enables propane and normal paraflins to be condensed with halooleflns. The interaction of propane and normal parailins with haloolefins is not catalyzed by Friedel-Crafts metal halides.

The process of this invention may be carried out ,in batch operation by placing a quantity of the saturated hydrocarbon and the catalyst in a reactor equipped with a mixing device, adding the chloroolenn, heating to a reaction temperature while mixing the contents of the react r,

2,sea,seo

cooling after a suitable period of-time, and recovering the condensation products.

Thepreferred method of operation is of the continuous type. In this method of operation the saturated hydrocarbon, the chloroolefin, and the catalyst are continuously charged to a reactor maintained at suitable conditions of temperature and pressure. The reactor may be an unpacked vessel or coil, or it may contain an adsorbent packing material such as lire brick, alumina, dehydrated bauxite. and the like, The condensation products are separated from the reactor eiiluent and the unconverted material may be recycled to the reaction zone.

Instead of separately adding the peroxide catalystto the reaction zone, I have found that it frequently is more desirable and economical-to form a catalyst in situ in the saturated hydrocarbon and then charge the resulting solution to the reaction zone together with the chloroolefln. Formation of the peroxide in the saturated hydrocarbon may be accomplished by auto-oxidation, 1. e., by heating the hydrocarbon while air is bubbled through it, preferably in the presence of a trace of peroxide formed in a previous autooxidation. Alternatively, the air may be passed through the hydrocarbon in the presence of an oxidation catalyst such as manganese stearate.

In the continuous methods of carrying out my process, the catalyst preferably is added continuously to the reactionzone, but if desired, it may be added intermittently.

In yet another mode of operation, the reactants and the peroxide are heated with water, with or without the addition of emulsifying agents. Contrary to what might be expected, the presence of water does not have a harmful effect on the reaction. Instead, the yield of desired product is actually increased. The reactions in the presence of water may be carried out in either batch or continuous types of operation.

The temperatures employed in the process of this invention should be at least as high as the initial decomposition temperature of the peroxy compound used as the catalyst. In the case of tertiary butyl perbenzoate, for example, the decomposition temperature is rather sharply de lined and is approximately C. On the other hand, benzoyl peroxide decomposes over a relatively wide temperature range. advantage is gained if the reaction is conducted at a temperature more than about C. higher b11131; the decomposition temperature of the cata s Saturated hydrocarbons condense with chlorooleilns in the presence of peroxy compound catalysts when the reactants are in the vapor phase as well as when they are in the liquid phase. However, "liquid phase operation is preferred, consequently, the pressure at which the reaction is conducted will be chosen accordingly.

The reaction times may be within the range of from slightly less than one minute to several hours. However, contact times of at least ten minutes usually are preferred.

The following examples are given to illustrate my invention but they are not introduced with the intention of unduly limiting the generally broad scope of said invention.

EXAMPLEI Usually little I aoeaeeo ers in a rotating autoclave of 850 cc. capacity. The reactants were heated at the designated temperatures, for four hours after which the product was cooled and recovered. The operating conditions and results are shown in the following table.

pressure sure). The yield of dichloride was 34% o! the theoreticaiibased on the trichloroethylene- 6 hexyli-ethylene, boiling at 71-72 C. ,at 2.6 mm.

(about 222-224 C. at atmospheric pres- 6 charged. The presence of water thus resulted in a 50% increase in yield (01. expt. No. 9).

Table 1 OONDENSATION 01" BATURhTED flYDltoflAlgg gflxY gll l OHLOROETHYLENEB IN THE PBESENOE'OF am. No 1 2 a 4 a a 1 a I o Ohloroolefln OIOH=OHO1 OlsC=UHCl :01 OgHlOh 0130b Hydrocarbon- 1041110 I Y nCsHn CtHt 101E" CaHe 104E": Q1Hu 01H loo i so 67 as e0 so u 1 e0 41 78 170 105 110 112 115 100 75 50 4 I8 l3 l8 :4 e5 .1 115 140 140 140 140 140 140 115 115 4 4 4 4 4 4 4 4 4 so 50 so so so 50 so so 50 83 97 75 117 100 118 112 78 70 Final..-- 52 52 49 50 52 57 v50 50 50 Total Liquid Pr0d., g -1-.. 90 66 165 05 87 68 5d 152 90 Chief Product: I

ormula i) (9 (0 Ave. B. P., 0--..-. 105 106 135 82 135 119 151 192 222 Yield, Moles 0. 13 0. 22 9. 05 0. 07 0. 21 0. 14 0. 09 0.12 0. 07 Yield. Per cent of Theoretical 21 35 7 10 46 81 19 23 l Trans-Dichloroethylene. 5 Di-tertiary-butyl peroxide. O4HrOH=CCh. I Cis-Diehloroethyiene. Methylgyclnhexane. 11 C H1CH=-00l,. 1 Mixture of cisand trans- C4H'- 1101. ll C;H1-C0l=C0l|.

dichloroethylene. I C|Hu-OH=CHOL I! C1H1r-CH=OHOL l Tertiary-Butyl perbenzoate. CsHr-CH=CHC1. C1H|rCH=CCl,. It will be noted that straight chain, branched EXAMPLE m chain, and cyclic paraflins were all readily condensed with the chlorooleiins. Of particular interest is the fact that normal pcntane and propane were reacted with chloroethylenes.

EXAMPLE II An experiment similar to expt. No. 9 of Example I was carried out in order to show the effect of water. A mixture of g. of trichloroethylene, g. of methylcyclohexane, 3 g. 01 tertiary-butyl perbenzoate and 100 g. of water was placed in a glass liner and heated in a rotating A number of attempts were made to condense tribromoethylene with various saturated hydrocarbons under a variety of operating conditions. Also, two experiments were made in which it was attempted to condense dibromoethylene with saturated hydrocarbons. These latter two experiments were made in order to obviate any objection that steric factors might be involved in the reactions with the tribromoethylene. The operating conditions and results are shown in the following table:

Table 2 Expt. No ll 12 i3 14 i5 16 17 Bromooieiin l ibumiw uuyieu 1,2-Dibromoethylene Hydrocarbon Mgthyl-Cyclon-Heptane.. Isobutane Propane Me thyI-Cyelo- Propane.

exane. exane. Peroxide Benzoyl Peroxide Di-t-Butyl t-Butyl Per- Benzoyl Pert-Butyl-Per- Peroxide. benzoate. oxide. benmate.

Reactants, g.:

Bromoolefins 66 50 43 43 22 38 Hydrocarbon... 51 25 50 105 100 23 70 Peroxide 5 5 6 6 6 3 6 Temperature, C 94 97 140 140 115 101 116 Duration, Hours. 7 9 4 4 4 10 4 Pressure, Atm

Initi 1 1 50 50 50 1 50 Maximum l 1 103 101 l Final at Room temperature l 1 50 50 50 1 50 Products, g.: V

Total Liquid 96 1 49 l 31 l 44 46 38 Higher Boiling 5 0 1 1 1 1 2 I 4 l 2 i I a 1 Consists of dark amber liquid and black deposit on liner wall.

I Dark amber liquid and black coating (crinkled and separated from wall of liner; insoluble in acetone and benzene).

I Dark amber liquid. 1 Product remaining in distillation flask,

after distillation of major portion of unreactcd hydrocarbon and polybromoethylene.

Dark amber liquid bottoms from distillation under 20 mm. pressure; includes tribromoethylene.

6 Product not washed before distillation. Includes benzoic acid.

g. (0.10 mole) of 1,1-dichloro-2-(methylcyclo- 75 It can be seen that substantially no reaction took 70 place in any of the experiments, even though some of the experiments were conducted at at: mospheric pressure under reflux conditions and the remainder were conducted in bombs under superatmospheric pressure.

Other experiments have shown that iodoole- 7 tins react in substantially the same manner as the bromooleii'ns. On the other hand, fluoroolefins react with saturated hydrocarbons in the presence of peroxide, but they donot ive the same type of products as do chlorooleflns. When poiyiiuorooleilns react with paraiilns or with cycloparamns no hydrogen fluoride is evolved and the resultant product is saturated. In addition, more than 1 molecule of the fluorooletin combines with 1 molecule of the saturated hydrocarbon, i. e., simple 1 to 1 condensation is not obtained as a major reaction product as in the case of chlorooleiins and saturated hydrocarbons. Therefore, it can be seen that the reaction that takes place with polychlorooleflns and saturated hydrocarbons in the presence of perox-y compound condensation catalysts is unique.

EXAMPLEIV A mixture of 51 g. of l,2-dichloro-3,3,3-triiluoro-l-propene, 145 g. of isobutane and 8 g. of di-tertiary-butyl peroxide was heated at 130- 140 C. in a glass liner in a rotating autoclave as described in Example I. Distillation oi the reaction product yielded g. (43% of the theoretical) of a trifluorochloroheptene. apparently 1,1,1 triiluoro-2-chloro-4,4-dimethyl-2-heptene, boiling at 56-57 C. at 121 mm. pressure and having a refractive index, n oi. 1.3832.

I claim as my invention:

1. A process for producing an unsaturated chlorinated hydrocarbon which comprises condensing, in the presence oi a peroxy compound catalyst and at 'a reaction temperature at least as high as the initial decomposition temperature of said catalyst, one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms and one molecular proportion of a polychlorooleiln having at least one chlorine atom attached to each of the doubly bonded caraseam bon atoms, said reaction temperature being sufiicient to split of! one molecular proportion of hydrogen chloride from the reaction mixture. V

2. A process for producing an unsaturated chlorinated hydrocarbon which comprises condensing, in the presence of an organic peroxide catalyst and at a reaction temperature at least as high as the initial decomposition temperature of said catalyst, one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms and one molecular proportion of a polychlorooleiin having at least one chlorine atom attached to each of the doubly bonded carbon atoms, said reaction temperatur being surilcient to split on one molecular proportion of hydrogen'chloride from the reaction mixture.

3. A, process for producing an unsaturated chlorinated hydrocarbon which comprises condensing, in the presence of a peroxy compound catalyst and at a reaction temperature at least as high as the initial decomposition temperature of said catalyst, one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms and one molecular proportion of a polychloromonoolefln having at least one chlorine atom attached to each of the doubly bonded carbon atoms, said reaction temperature being suiiicient to split oi! one molecular proportion 01 hydrogen chloride from the reaction mixture.

4. A process which comprises reacting one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms with one molecular proportion of a polychloroolefln having at least one chlorine atom attached to 8 each of the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature oi the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature beinl suiiicient to split oi! one molecular proportion of hydrogen chloride from the reaction mixture. 4

5. A process which comprises reacting one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms with on molecular proportion ot a polychloromonooleiin having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of an organic peroxide condensation catalyst at a condensation temperature at least as high as theinitial decomposition temperature or the catalyst and a pressure such that a substantial portion 01' the reactants is in the liquid phase, said condensation ternperature being suflicient to split oi! one molecular proportion of hydrogen chloride from the reaction mixture.

6. A process which comprises reacting one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms with one molecular proportion oi a polychloroethylene in which each of the doubly bonded carbon atoms has at least one chlorine atom attached thereto in the presence 01' a peroxy compound condensation catalyst and at a condensation temperature at least as high as the initial decomposition temperature of the catalyst, and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being sumcient to split 01! one molecular proportion oi hydrogen chloride from the reaction mixture.

7. A process which comprises reacting one molecular proportion of a cycloparaiiin having at least five carbon atoms in the ring with one molecular proportion of a polychloroethylene havin at least one chlorine atom attached to each of the doubly bonded carbon atoms with a polychloroethylene having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants is in the'liquid phase, said condensation temperature being-suillcient to split of! one molecular proportion of hydrogen chloride from the reaction mixture.

8. A process which comprises reacting one molecular proportion of a cycloparailin having at least five carbon atoms in the ring with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of an organic peroxide condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being suillcient to split oi! one molecular proportion of hydrogen chloride from the reaction mixture.

9. A process which comprises reacting one molecular proportion of a paramn containing more. than two carbon atoms with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each of of a peroxy compound condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature of the cat-- alyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being sufllcient to split 011 one molecular proportion of hydrogen chloride from the reaction mixture.

10.'A process which comprises reacting one molecular proportion of a straight-chain paraffln containing more than two carbon atoms with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature 01' the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being sufficient to split off one molecular proportion of. hydrogen chloride from the reaction mixture.

11. A process which comprises reacting one molecular proportion of an isoparamn with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being suflicient to split of! one molecular. proportion of hydrogen chloride from the reaction mixture.

12. A process which comprises reacting one molecular proportion of a paramn containing more than two carbon atoms with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each of the doubly bonded carbon atoms in the presence 'of an organic peroxide condensation catalyst at a condensation temperature at least as high as the initial decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being sufllcient to split of! one molecular proportion of hydrogen chloride from the reaction mixture.

13. A process which comprises reacting one molecular proportion of isobutane with one molecular proportion of a polychloroethylene having at least one chlorine atom attached to each oi the doubly bonded carbon atoms in the presence of a peroxy compound condensation catalyst at a condensation temperature at least as high as the decomposition temperature of the catalyst and a pressure such that a substantial portion of the reactants is in the liquid phase, said condensation temperature being suflicient to split 01! one molecular proportion of hydrogen chloride from the reaction mixture.

14. A process which comprises reacting one molecular proportion of isobutane with one molecular proportion of trichloroethylene in the presenceof a peroxy compound condensation catalyst at a condensation temperature at least as high as the decomposition temperature of the catalyst, said condensation temperature being suflicient to split off one molecular proportion of hydrogen chloride from the reaction mixture.

15. A process which comprises reacting one molecular proportion of a saturated hydrocarbon containing more than two carbon atoms with one molecular proportion of a polyohloromonoolefin, in which each of the doubly bonded carbon atoms has at least one .chlorine atom attached thereto, in the presence of a peroxy compound condensation catalyst and water and at a condensation temperature at least as high as the initial decomposition temperature of the cata- .the initial decomposition temperature of said catalyst, said condensation temperature being sufllcient to split oil one molecular proportion of hydrogen chloride from the reaction mixture.

LOUIS scmmaunc.

REFERENCES crrEn The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,411,159 Hanford Nov. 19, 1946 2,440,800 Hanford et ai. May 4, 1948 2,449,360

Austin .a Sept. 14. 1948 

1. A PROCESS FOR PRODUCING AN UNSATURATED CHLORINATED HYDROCARBON WHICH COMPRISES CONDENSING, IN THE PRESENCE OF A PEROXY COMPOUND CATALYST AND AT A REACTION TEMPERATURE AT LEAST AS HIGH AS THE INITIAL DECOMPOSITION TEMPERATURE OF SAID CATALYST, ONE MOLECULAR PROPORTION OF A SATURATED HYDROCARBON CONTAINING MORE THAN TWO CARBON ATOMS AND ONE MOLECULAR PROPORTION OF A POLYCHLOROOLEFIN HAVING AT LEAST ONE CHLORINE ATOM ATTACHED TO EACH OF THE DOUBLY BONDED CARBON ATOMS, SAID REACTION TEMPERATURE BEING SUFFICIENT TO SPLIT OFF ONE MOLECULAR PROPORTION OF HYDROGEN CHLORIDE FROM THE REACTION MIXTURE. 